Certain phosphorus acid esters

ABSTRACT

Organic phosphorus compounds of the formula   wherein R1 represents C1-C5-alkyl, R2 represents C1-C2-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, C1-C5alkoxy-C1-C5-alkyl or C1-C5-alkylthio-C1-C5-alkyl, R3 represents C1-C5-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4alkylthio-C1-C4-alkyl or C3-C4-alkenyl, and X and Y each represent oxygen or sulphur, processes for their preparation and their use in pest control.

United States Patent [191 Rufenacht Nov. 18, 1975 [73] Assignee:Ciba-Geigy Corporation, Ardsley,

[22] Filed: Oct. 9, 1973 [21] App]. No.: 404,572

[30] Foreign Application Priority Data Oct. 6, 1972 Switzerland 14695/72July 31, 1973 Switzerland 11147/73 [52] US. Cl. 260/302 E; 474/200 [Sl]Int. Cl. C07D 285/12 [58] Field of Search 260/302 E [56] ReferencesCited UNITED STATES PATENTS 2,706,194 4/1955 Morris et al 260/302 E3,239,532 3/1966 Rufenacht 260/302 E Primary Examiner-Richard J.Gallagher Attorney, Agent, or Firm-Frederick l-l. Rabin 57 ABSTRACTOrganic phosphorus compounds of the formula wherein R represents C -C-alkyl, R represents C -C -alkyl, C -C -alkenyl, C -C -alkynyl, C -C-alkoxy-C C -alkyl or C -C -alkylthio-C -C -alkyl, R represents C -C-alkyl, C -C -alkoxy-C -C alkyl, C -C -alkylthio-C -C -alkyl or C -C-alkenyl, and

X and Y each represent oxygen or sulphur, processes for theirpreparation and their use in pest control.

9 Claims, No Drawings CERTAIN PHOSPHORUS ACID ESTERS The presentinvention relates to organic phosphorus compounds, to processes fortheir preparation, and to their use in pest control.

The phosphorus compounds correspond to the formula wherein R representsC -C -alkyl,

R represents C -C -alkyl, C -C -alkenyl, C -C -alkynyl, C -C -alkoxy-C-C -alkyl or C,-C -alkylthio-C -C alkyl,

R represents C -C -alkyl, C -C -alkoxy-C -C -alkyl, C -C -alkylthio-C,-C-alkyl or C -C -alkenyl, and

X and Y each represent oxygen or sulphur.

The alkyl, alkenyl, alkynyl, alkoxyalkyl and alkylthioalkyl groupsdenoted by R to R can be straight-chain or branched. Examples of suchgroups are: methyl, methoxy, methoxymethyl, methylthio,me'thylthiomethyl, ethyl, ethoxy, ethoxyethyl, ethylthio,ethylthioethyl, propyl, isopropyl, n-, i-, sec.-, tert.-butyl, n-pentyl,nhexyl, and their isomers.

Compounds of formula I which are preferred on account of theireffectiveness are those wherein R represents methyl or ethyl,

R represents C -C -alkyl, methoxyethyl or ethoxyethyl,

R represents C -C -alkyl,

X represents oxygen, and

Y represents oxygen or sulphur.

The compounds of formula I are prepared by methods known per se, e.g. asfollows:

In the formulae ll, Ill and IV, the symbols R R R X and Y have themeanings given for formula I, and Me stands for a monovalent metal,particularly an alkali metal.

Suitable acid-binding agents are: tertiary amines, e.g. trialkylamines,pyridine or dialkylanilines; inorganic bases such as hydroxides;carbonates and bicarbonates of alkali metals or alkaline-earth metals.

It is sometimes necessary that catalysts be used in the reactions, suchas, e.g. copper or copper chloride.

The reactions (a) and (b) are performed at a temperature of O-l 20C,preferably between and 70C, at normal pressure and in solvents ordiluents that are inert to the reactants. The following, for example,are suitable as solvents or diluents: ethers and ethereal compounds,such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane ortetrahydrofuran; amides such as N,N-di-alkylated carboxylic acid amides;aliphatic, aromatic as well as halogenated hydrocarbons, especiallybenzene, toluene, xylenes, chloroform or chlorobenzene; nitriles such asacetonitriles; DMSO; ketones such as acetone, methyl ethyl ketone, ormixtures of such solvents with water.

The starting materials of formulae II, III and IV are known, and can beprepared my methods analogous to known methods.

The compounds of formula I have a broad biocidal action and aretherefore suitable for the control of diverse plant and animal pests.They possess however, in particular, insecticidal and acaricidalproperties, and

can be used against all development stages, such as, e.g.

eggs, larvae, pupae, nymphs and adults of insects and members of theorder acarina, such as, e.g. against insects of the families:Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae,Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae,Pseudococcidae, Scarabacidae, Dermestidae, Coccinellidae, Tenebrionidae,Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae,Culcidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridaeand Pulicidae, as well as acarids of the families: lxodidae, Argasidae,Tetranychidae and Dermanyssidae.

The insecticidal or acaricidal action can be apprecia- .bly broadenedand adapted to suit the given circumstances by the addition of otherinsecticides and/or acaricides. Suitable additives are, for example:

organic phosphorus compounds,

derivatives of nitrophenols,

formamidines,

ureas,

carbamates, and

chlorinated hydrocarbons.

The active substances of formula I are suitable also for the control ofmembers of the division thallophyta, such as, e.g. viruses, bacteria andfungi. They thus have fungicidal properties rendering them effectiveagainst phytopathogenic fungi in various cultivated crops, such as corn,maize, vegetables, ornamental plants, fruit trees, grape vines, fieldfruits, etc. With the new active substances, fungi occurring on fruits,blossom, foliage, stalks tubers and roots can be checked or destroyed,whereby parts of plants subsequently growing remain immune against suchfungus infestation. The active substances of formula I are effectiveespecially against phytopathogenic fungi belonging to the followingclasses: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDenteromycetes.

Futhermore, the new active substances are used for the treatment ofseed, fruits, tubers, etc. for protection against fungus infections dueto, for example, smut fungus of all varieties, such as Ustilaginales,and for the control of phytopathogenic nematodes.

The compounds of formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives maybe solid or liquid, and correspond to the substances common informulation practice, such as, e.g. natural and regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers. I

For application, the compounds of formula I can be processed into theform of dusts, emulsion concentrates, granulates, dispersions, sprays,or solutions, the

formulation of these preparations being effected in a 19.5 parts ofChampagne chalk, manner commonly known in practice. Also to be men- 28,1art of kaolim tioned are cattle dips and spray races, in which aqueousPreparations are 25 parts of active substance,

The agents according to the invention are produced 5 25 Parts fisooctylphenoxypolyoxyethylene in a manner known per se by the intimatemixing andethanol, /or grinding of active substances of formula 1 withthe 17 parts of Champagne chalk/hydroxyethyl ceuu suitable carriers,optionally with the addition of dislose mixture (1:1) persing agents orsolvents which are inert to the active 83 parts of Sodium aluminiumSilicate,

substances. The active substances can be obtained and used in thefollowing preparation forms:

solid preparations: dusts, scattering agents, granud lates, coatedgranulates, impregnated granulates and homogeneous granulatesj liquidpreparations:

a. water dispersible active substance concentrates:

wettable powders, pastes, emulsions;

Solutions. hyde condensate.

The content of active substance in the described 82 Parts of kaolinagemsi between 1 and 95%; it is to be mentioned in 20 The active substancesare intimately mixed, in suitl6.5 parts of kieselguhr, 46 parts ofkaolin.

10 parts of active substance, 15 3 parts of a mixture of the sodiumsalts of saturated fatty alcohol sulphates, 5 parts ofnaphthalenesulphonic acid/formaldehi connection h i h case f li i f anable mixers, with the additives, the mixture being then aeroplane, or bymeans of other suitable devices, conground in the appropriate mills androllers. wettable centrations of up to 99.5% can be employed, or evenpowders are obtained which can be diluted with water the pure activesubstance. to give suspensions of any desired concentration.

The active substances of formula I can be prepared, Emulsifiableconcentrates: for example, as follows: The following substances are usedto produce (a) a Dusts: 10% and (b) a 25% emulsifiable concentrate: Thefollowing substances are used in the preparation of (a) a 5% dust and(b) a 2% dust: 10 parts of active substance,

x 3.4 parts of epoxidised vegetable oil,

5 Parts of actve Substance 13.4 parts of a combination emulsifierconsisting of 95 parts of talcum; fatty alcohol polyglycol ether andalkylarylsulphonate calcium salt,

2 parts of actwe SPbStanCeZ 40 parts of dimethylformamide, 1 part ofhighly dispersed silicic acid, 43 2 parts of xylene. 97 parts of talcum.b The active substances are mixed and ground with the carriers 25 partsof active substance,

Granulate: 2.5 parts of epoxidised vegetable oil, The followingsubstances are used to produce a 5% 40 lo parts of analkylarylsulphonate/fany alcoholpolyglycol ether mixture 5 parts ofdimethylformamide, 57.5 parts of xylene. From these concentrates it ispossible to produce, by dilution with water, emulsions of any desiredconcengranulate:

5 parts of active substance, 0.25 parts of epichlorhydrin, 0.25 parts ofcetyl polyglycol ether, 3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 0.8 mm). nation- The activesubstance is mixed with epichlorhydrin p y and dissolved with 6 parts ofacetone; the polyethylene The fol o ing constituents are used to preparea 5% glycol and cetyl polyglycol ether are then added. The spray:solution thus obtained is sprayed on to kaolin, and the 5 parts ofactive substance, acetone subsequently evaporated off in vacuo. 1 partof epichlorhydrin,

wettable powder: 94 parts of ligroin (boiling limits 160190C). Thefollowing constituents are used for the preparation of (a) a 40%, (b)and (c) a 25%, and (d) a 10% EXAMPLE 1 wettable powder: Preparation fO,S-dimethyl-S-(S-methoxy-l ,3 ,4-thiadiazol- 40 Parts of activeSubstance, 2(3H)-on-3-yl-methyl)-dithiophosphate 5 parts of sodiumlignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54parts of silicic acid.

A solution of 36 g of 3-chl0romethyl-5-methoxy- 0l,3,4-thiadiazol-3(3l-l)-one in ml of acetone is added dropwise to amixture of 49 g of potassium salt of O,S-dimethyl-dithiophosphoric acidand ml of acetone, and stirring maintained for 16 hours at roomtemperature. The acetone is then distilled off, and 100 ml 65 of wateradded to the residue; the precipitated oil is iso- 25 parts of activesubstance,

4.5 parts of calcium lignin sulphonate 1.9 parts of Champagnechalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulpholated by extraction withether, and subsequently subnate, jected to molecular distillation toobtain the compound 19.5 parts of silicic acid, of the formula as paleyellow oil having a boiling point of l30C/0.008

Torr. I Calculated: N, 9.27; P, 10.27; S, 31.82%. Found: N, 8.83; P,10.06; S, 32.21%. Further compounds preparedin an analogous manner arelisted in the following table:

A. Insecticidal stomach poison action Cotton and potato plants weresprayed with a 0.05%

aqueous active-substance emulsion (obtained from a 10% emulsifiableconcentrate).

After the drying of the obtained coating, Spodoptera Iitoralis orHeliothis virescens larvae L were placed onto the cotton plants, andColorada beetle larvae (Leptinotarsa decemlineata) onto the potatoplants. The test was carried out at 24C with relative humidity.

The compounds according to Example 1 exhibited in the above test a goodinsecticidal stomach poison action against Spodopzera litoralis,Heliothis and Leptinotarsa decemlineata larvae.

B. Systemic insecticidal action In order to determine the systemicaction, rooted bean plants (Vicia faba) were placed into a 0.0l% aqueousactive-substance solution (obtained from a 10% emulsifiableconcentrate). After a period of 24 hours, bean aphids (Aphis fabae) wereplaced onto the parts of the plants above the soil. The insects wereprotected by a special device from the effects of contact and of gas.The test was carried out at 24C with relative humidity.

In the above test, the compounds according to Example lex hibit ed'asystemic action against Aphis fqbaef Example 3 j Action againstChilq-suppre'ssalis Rice plants of the type Caloro were planted, 6plants per pot, in plastic pots having a top diameter of 17 cm, andgrown to a height of ca. 60 cm. infestation with Chilo suppressalislarvae (L,; 3-4 mm long) was carried out 2 days after application of theactive substance in granular form (amount applied 8 kg of activesubstance per hectare) to the paddy water. The evaluation of theinsecticidal action was made 10 days after application of the granules.

The compounds according to Example 1 were effective against Chilosuppressalis in the above test.

Example 4 Action against ticks A. Rhipicephalus bu r sa v p In eachcase, 5 adult ticks or 50 tick larvae were placed into a small glasstest' tube, and the test tubes then immersed for 1 to 2 minutes in 2 mlof an aqueous emulsion from a dilution series of 100, 10, l and 0.1 ppmof test substance. The tubes were then sealed with a standardised cottonplug, and inverted'so that the active substance emulsion could beabsorbed by the cotton wool. I

An evaluation in the case of the adults was made after 2 weeks, and inthe case of the larvae after 2 days. There were two repeats for eachtest.

B.- B00philus microplus (larvae) v With a dilution series analogous tothat in Test A, tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (resistance is with respect to diazinoncompatibility). v

Compounds according to Example 1 were effective in these tests againstadults and larvae of Rhipicephalus bursa and against sensitive andOP-resistance larvae, respectively, of Boophilus microplus.

Example 5 Acaricidal action g Phaseolus vulgaris (plants) were infested,12 hours before the test for acaricidal action, with an infested pieceof leaf from a mass culture of Tetranychus urticae. The transferredmobile stages were sprayed with the emulsified test preparations from achromatography-sprayer in a manner ensuring no running off of the sprayliquor. An assessment was made after 2 to 7 days, by examination under abinocular, of the living and of the dead larvae, adults and eggs, andthe results expressed in percentages. The treated plants were keptduring the holding time in greenhouse compartments at 25C.

The compounds according to Example 1 were effective in the above testagainst adults, larvae and eggs of Tetranychus urticae.

Example 6 Action against soil nematodes In order to test the actionagainst soil nematodes the active substances were added, in theconcentration stated in each case, to soil infested withroot-gallnematodes (Meloidogyne arenaria), and the whole intimatelymixed. In the one test series, tomato seedlings 7 were plantedimmediately afterwards in the thus prepared soil, and in the other testseries tomatoes were planted after a waiting time of 8 days.

For an assessment of the nematicidal action, the galls present on theroots were counted 28 days after planting and sowing, respectively.

Active substances according to Example 1 exhibited in this test a goodaction against Meloidogyne arenaria.

We claim:

l. A compound of the formula 10 l i T R.0

\PSCH -N N R,s 2

wherein R represents methyl or ethyl, R represents methoxyethyl orethoxyethyl, R represents C -C alkyl, and Y represents oxygen orsulphur. 2. Compound according to claim 1 of the formula O=C -OCH HPSCH,-N CH OCJ-LS 3. Compound according to claim 1 of the formula 4.Compound according to claim 1 of the formula 5. Compound according toclaim 1 of the formula 6. Compound according to claim 1 of the formula7. Compound according to claim 1 of the formula 8. Compound according toclaim 1 of the formula 9. Compound according to claim 1 of the formula

1. A COMPOUND OF THE FORMULA
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